201007165 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種例如在半導體業界或電子零件業界 中’適合於利用雷射消熔裝置與電漿分析裝置分析在金 屬、半導體、陶瓷、玻璃、塑膠等材料表面之微量添加元 素或微量雜質元素等之方法及系統。 【先前技術】 例如在歐洲，依據RoHS規範，禁止電子零件等材料中 含有鉛、汞、鎘、鉻等元素，故為了其確認，利用雷射消 熔裝置對試樣照射雷射光，使其試樣之一部分變成微粒子 (氣溶膠），藉由載運氣體將該微粒子導入於感應耦合電漿 質量分析裝置（ICP-MS)、感應耦合電漿發光分析裝置 (ICP-AES)、微波感應電漿質量分析裝置（mip_ms)、微波 感應電漿發光分析裝置（MIP_AES)等之電漿分析裝置，施 行该材料之微量添加元素或微量雜質元素等之分析（參照 專利文獻1、專利文獻2)。使用此種分析系統，可—次分 析試樣中所含之複數種微量元素。 以往，在如上述之分析系統中，直接連結雷射消熔裝置 與電漿分析裝置，將雷射消熔之際之環境氣體直接導入電 漿分析裝置作為微粒子之載運氣體。即，在使用以往之雷 射消熔裝置與電漿分析裝置之系統中，不更換載運氣體而 將微粒子由雷射消熔裝置搬送至電漿分析裝置。又，已知 以氦氣或氬氣作為雷射消熔之際所使用之載運氣髏，且已 知以氬氣作為電漿分析之際所使用之載運氣體。 141739.doc 201007165 .[專利文獻1]日本特開2004-325390號公報 . [專利文獻2]日本特開2006-153660號公報 【發明内容】 [發明所欲解決之問題] ; 在雷射消熔中，使用氦氣作為載運氣體之情形，其比較 的熱傳導性咼於氬氣，故在雷射照射中呈現高溫之區域會 增大。因此’藉由雷射消溶所產生之微粒子會變小，故可 減低微粒子對雷射消熔所形成之試樣之凹痕周邊或載運氣 • 體流路内面之附著，增多搬送至電漿之微粒子而提高分析 感度。另外，微粒子增大時，難以施行在電漿内之分解、 離子化，故微粒子變小時，可提高在電漿分析裝置内之原 子化、離子化之效率，並提高分析感度及來自電漿之信號 之穩定性。 但，因以下之理由，在電漿分析之際，最好使用氬氣作 為載運氣體。即，與氬氣相比，氦氣之離子化電壓較高， 為保持電漿而離子化所需之電力會增大，分析裝置之負荷 ® 也會增大，且電漿中之離子密度會降低。另外，使用氦氣 時，與氬氣相比，電漿會變得不穩定，分析時之最適測定 • 條件之選定較為繁雜，難以高感度且高精度而穩定地測定 複數種元素，故操作性低而損及分析之迅速性、簡便性。 即，以往，使用雷射消熔裝置與電漿分析裝置之分析之最 適化會因載運氣體之特性而受到妨礙。 又’起因於試樣之構成成分，而有因雷射消熔而產生導 致電漿分析感度之降低及妨礙測定之氣體成分（例如s 〇 2等 141739.doc 201007165 硫化物）之虞。 本發明之目的在於提供一種可解決如上述之問題之 方法及分析系統。 [解決問題之技術手段] 本發明之分析方法之特徵在於以下之點：在含第〗氣體 之環境氣體中，藉由雷射消溶裝置使試樣變成微粒子；以 前述第〗氣體作為載運氣體，將前述微粒子由前述雷射消 熔裝置搬送至氣體置換裝置；藉由前述氣體置換裝置，將 前述載運氣體之至少一部分由前述第！氣體氣體地置換成❹ 第2氣體；藉由該經氣體置換之載運氣體，將前述微粒子 2前述氣體置換裝置搬送至電漿分析裝置；藉由前述電漿 分析裝置分析前述微粒子之構成元素。 依據本發明之分析方法，使用第1氣體作為雷射消熔之 際之试樣之環境氣體，可藉由含有由第丨氣體被置換之第2 氧體之載運軋想，將微粒子搬送至電漿分析裝置之電漿。 又，在其雷射消熔中，即使起因於試樣之構成成分而產 生導致電漿分析感度之降低及妨礙測定之氣體成分也可❿ 藉由氣體置換裝置之氣體置換除去其氣體成分。 本發明之分析系統之特徵在於以下之點：具備：第1氣 體供應源’其係供應第1氣體；雷射消熔裝置，其係在含 ' 由刚述第1氣體供應源供應之前述第1氣體之環境氣體中， . 藉由雷射消熔使試樣變成微粒子，且其具有使作為載運氣 體之則述第1氣體與前述微粒子同時流出之第1載運氣體出 口並具備供應第2氣體之第2氣體供應源；氣體置換裝置， 141739.doc -6 - 201007165 其係具有與前述微粒子同時導入由前述第1載運氣趙出口 流出之前述第1氣體用之第1載運氣體入口、導入由前述第 2氣體供應源被供應之第2氣體用之第2氣體入口、將前述 載運氣體之至少一部分由前述第丨氣體氣體置換成前述第2 氣體之氣體置換部、及使該經氣體置換之載運氣體與前述 微粒子同時流出之第2載運氣體出口；及電漿分析裝置， 其係具有與前述微粒子同時導入由前述第2載運氣體出口 流出之前述載運氣體用之第2載運氣髖入口，產生用以分 析與則述載運氣體同時被導入之前述微粒子之構成元素之 分析用電漿。 依據本發明之分析系統，可實施本發明方法。 在本發明中，例如，前述第1氣體以使用氦氣為宜，前 述第2氣體以使用氬氣為宜。使用比較的熱傳導性較高之 氦氣作為第1氣體時，在雷射消熔中產生之微粒子會變 小，故可減低微粒子對試樣之凹痕週邊或載運氣體流路内 面之附著，增多搬送至電漿之微粒子，並提高在電漿分析 裝置内之原子化、離子化之效率，提高分析感度及來自電 漿之信號之穩定性。又，使用氬氣作為第2氣體時，可藉 由含離子化電壓較低之氬氣之載運氣體，將微粒子導入電 漿，故可降低為保持電漿而離子化所需之電力、分析裝置 之負荷，提南電漿中之離子密度，使電衆穩定，並可容易 施行分析時之最適測定條件之選定。 【實施方式】 [發明之效果] 141739.doc 201007165 依據本發明’在對藉由雷射消熔產生之微粒子進行電漿 分析之際’可防止分析條件之最適化受到搬送微粒子之載 運氣體之特性或雷射消熔產生之氣體成分所妨礙，不損及 操作性、迅速性、簡便性而可高感度且高精度而穩定地測 定複數種元素。 圖1所示之分析系統丨係包含第丨氣體供應源2、雷射消熔 裝置3、第2氣趙供應源4、氣體置換裝置5、電漿分析裝置 6及氣體附加裝置7。 在本實施型態中，第1氣體供應源2係用以供應氦氣作為 第1氣體’例如係由儲氣瓶所構成。 雷射消熔裝置3可使用公知之雷射消熔裝置，具有出射 雷射束L之雷射照射部3a、與收容試樣〇1之試樣室3b。第1 氣體係自第1氣體供應源2經由氣體出口 3a，被供應至試樣室 3b内。在試樣室3|5内，在含第1氣體之環境氣體中，使雷 射束L照射於試樣α之表面’藉此’施行試樣α之雷射消溶 而使試樣α之一部分變成微粒子。為了以第丨氣體作為藉由 雷射消溶而產生之微粒子之載運氣艘而使其與微粒子同時 由試樣室3b流出’在試樣室3b形成第1載運氣體出口 3 在本實施型態中’第2氣體供應源4係用以供應氬氣，例 如係由儲氣瓶所構成。 如圖2所示，氣趙置換裝置5可使用公知之氣體置換裝 置’係包含橫剖面圓形之直管之内管52、覆蓋内管52之橫 剖面圓形之直管之外管53 ’内管52之兩端係由外管53突 出’外管53之兩端附近逐次變成小徑而密接於内管52之外 141739.doc -8 - 201007165 -周。 . 内管52係具有形成於一端之第1載運氣體入口 52a、形成 於另一端之第2載運氣體出口 52b、及第1載運氣體入口 52a 與第2載運氣體出口 52b之間之内侧氣體流路52c。第1載運 氣體入口 52a係經由配管（省略圖不）連接於雷射消溶裝置3 之第1載運氣體出口 3a’’藉此，使由第！載運氣體出口 3ai 流出之第1氣體與微粒子同時由第1載運氣體入口 52a導入 氣體置換裝置5。 • 外管53具有形成於一端附近之周壁之第2氣體入口 53a、 形成於另一端附近之周壁之排氣出口 53b、及第2氣體入口 53a與排氣出口 53b之間之外側氣體流路53c。第1載運氣體 入口 52a、第2載運氣體出口 52b、第2氣體入口 53a、及排 氣出口 5 3 b係被配置成使在内側氣體流路5 2 c之氣趙流動方 向與在外侧氣體流路53c之氣體流動方向呈現互相相反方 向。第2氣體供應源4係經由配管（省略圖示）連接於第2氣體 入口 53a。藉此’由第2氣體入口 53a’將第2氣體供應源4 所供應之第2氣體導入至氣體置換裝置5。 覆蓋内管52之内側氣體流路52c之周壁之兩端間部位係 . 形成為多孔性隔牆52A ’可藉由第1氣體與第2氣體之分歷 差所引起之擴散，使第1氣體向内侧氣體流路52c外移動， 並使第2氣趙向内側氣體流路5 2 c内移動。内側氣體流路 52c與外側氣體流路53c之壓力差’即，内側氣體流路52c 之内外壓力差所引起之經由多孔性隔牆52A之氣體移動可 被多孔性隔牆52A實質地阻止。因此，第1氣體與微粒子同 H1739.doc -9- 201007165 時由第1載運氣艘入口 52a被導入内管52内作為載運氣體’ 並在多孔性隔牆52A所包圍之内側氣體流路52c流動’第2 氣體由第2氣體入口 53a被導入外管53 ’在多孔性隔牆52A 之周圍之外側氣體流路53c向與第1氣體之流動方向相反方 向流動，以施行氣體置換。 即，藉由第1氣體與第2氣艎之分壓差產生之擴散，換言 之，以内侧氣體流路52c之内外之第1氣體與第2氣體之溫 度差為推進力，使第1氣體之大部分經由多孔性隔牆52A而 向内側氣體流路52c外移動，並使第2氣體之一部分經由多 孔性隔牆52A而向内側氣體流路52c内移動。在内側氣體流 路52c，隨著由第1載運氣體入口 52a流向第2載運氣體出口 52b，第1氣體之濃度會逐漸降低，同時第2氣體之濃度會 逐漸增加，在外側氣體流路53c，隨著由第2氣體入口 53a 流向排氣出口 53b ’第2氣體之濃度會逐漸降低，同時第1 氣體之濃度會逐漸增加。因此，可將在載運氣體之第1氣 體實質上全部置換成第2氣體。 又’也可不將内管52内之第1氣體之一部分置換成第2氣 體，而使不影饗電漿分析之程度之微量之第1氣體由第2載 運氣體出口 52b流出。藉由適宜地設定多孔性隔牆52A之各 孔徑、氣孔率、壁厚、管徑、長度、形狀、外管53之内 徑、形狀、第1氣體及第2氣體之流量等，可將由第2載運 氣體出口 52b流出之第1氣鳢控制在對電漿分析裝置6之分 析不會造成不良影響之極限量以下。即，由多孔性隔踏 52A所構成之氣體置換部只要能夠將微粒子之栽運氣體之 141739.doc -10 - 201007165 至少一部分由第1氣體置換為第2氣體即可。 • 因此’多孔性隔牆52A可構成將微粒子之載運氣體之至 少一部分由第1氣體置換為第2氣體之氣鱧置換部。又，内 管52之第2載運氣體出口 52b係使被氣艎置換而大部分為第 2氣體之載運氣體與微粒子同時由氣體置換部流出。原來 為載運氣體之第1氣禮、與未被置換成第1氣體之剩下之第 2氣體則由排氣出口 53b流出作為排出氣體《此際，在内側 氣體流路52c之微粒子中’其徑超過多孔性隔牆52A之外徑 • 者會穿透各孔，或不被各孔所俘獲，又在其孔徑以下者也 由於擴散速度慢於氣體，且擴散氣體之氣流之慣性力非常 弱’故大部分之微粒子不會向外侧氣體流路53c移動而會 由第2載運氣體出口 52b流出。故與第1氣體同時被導入之 微粒子不會減少或損失’可與第2氣體同時供應至電襞分 析裝置6 » 多孔性隔牆52A之各孔徑係被設定成可阻止因在内侧氣 體流路52c之壓力與在外側氣體流路53c之壓力之差而引起 之經由多孔性隔牆S2A之氣體移動，實質上以〇 8 μιη〜 0.001 μιη為宜。為防止氣體置換效率之降低而導致裝置大 • 型化，各孔徑係設定於〇_〇〇1 μιη以上，較好為〇〇〇2 μιη以 上，更好為0.02 μιη以上，為使微粒子穿透各孔，或防止 其被各孔所俘獲而降低分析精度，或因壓力差而發生氣體 移動，δ又疋於〇·8 μιη以下，較好為〇5 μιη以下，更好為 μιη以下。在多孔性隔牆52Α中，不影響氣體置換作用之程 度之微量之數之孔徑也可設定於〇8 μπι〜〇〇〇1 μιη之範圍 141739.doc 201007165 外’實質上只要設定於〇_8 μη!〜〇·〇〇1 pm即可。多孔性隔輪 52Α之氣孔率雖無特別限制，但從氣鱧置換效率及機械的 強度之觀點言之，以40%〜80%為宜。 多孔性隔牆52Α之材質只要符合上述條件，則無特別限 制’以石英等玻璃或陶瓷等為宜，例如可使用多孔質玻璃 (Shirasu porous glass，SPG)。内管52之兩端附近部位 52B、52C之内外徑與多孔性隔牆μα相等而圓滑地結合於 此。又’既可將覆蓋内側氣體流路52c之周壁全體形成作 為多孔性隔牆5 2 A ’也可將覆蓋内側氣體流路5 2 c之至少一 部分之部位形成作為多孔性隔牆52Αβ内管52之兩端附近 部位52Β、52C與外管53之材質並無特別限制，也可由複 數相異之材質構成，從加工容易性及導入於内管52之第1 氣體之加熱容易性或耐熱性之觀點言之，以使用金屬、陶 瓷、玻璃為宜，以形成作為如陶瓷或石英玻璃之玻璃為 宜。 必要時，也可在氣體置換裝置5附加加熱機構（省略圖 示）。加熱機構並無特別限制，例如可由捲繞在外管5 3之 周圍之帶狀加熱器或配置在外管53之周圍之紅外燈所構 成’此情形’也可設置控制内外管52、53内之溫度用之溫 度感測器與依照檢測溫度控制加熱機構之溫度控制裝置。 電衆分析裝置6可使用公知之電漿分析裝置，在本實施 型態中’具備有電漿喷燈61與分析部62作為ICP-MS。電 漿分析裝置6之種類並無特別限制，例如也可使用lcp_ AES、MIP-MS、MIP-AES。電漿喷燈61具有中心管61a， 141739.doc 201007165 中心管61a之一端形成作為第2載運氣體入口 61a，。由氣體 置換裝置5之第2載運氣體出口 52b流出之載運氣體係與微 粒子同時由第2載運氣體入口 61a，被導入電漿分析裝置6。 含由中心管61a被導入之微粒子之氣體係藉由圖外高頻線 圈等而變成微粒子之構成元素之分析用電漿P，並在分析 部62施行該構成元素之質量分析。又，產生電漿p用之電 漿氣體可由氣體導入口 6Γ導入電漿喷燈61，電漿氣體以使 用與第2氣艘相同之氣體為宜。 氣體附加裝置7係在氣體置換裝置5與電漿分析裝置6之 間附加載運氣體。即，氣體附加裝置7係具有第1導管71、 連接於第1導管71之第2導管72、質量流量控制器（MFC)或 流量控制閥等之流量控制器73、第3氣體供應源74、及壓 力調整部75 » 第1導管71之一端開口 71’連接於電漿分析裝置6之第2載 運氣體入口 61a’。第1導管71内形成有節流部71a、與連結 於節流部71 a之出口之擴散段71b。第1導管71之另一端開 口 71 ”經由流量控制器73連接於第3氣體供應源74。第2導 管72之一端72,經由壓力調整部75之第1管75a通至氣體置換 裝置5之第2載運氣體出口 52b，第2導管72之另一端72"通 至節流部71 a之出口附近之載運氣體之喷出區域。 在本實施型態中，第3氣體供應源74係用以供應被加壓 作為載運氣體之氬氣，例如係由儲氣瓶所構成》依據第3 氣體供應源74所供應之氬氣由節流部71 a噴出引起之壓力 頭之降低’將由氣體置換裝置5之第2載運氣體出口 52b流 141739.doc 13 201007165 出之載運氣體吸引至第1導管71内。即，氣體附加裝置7係 構成吸氣器。藉此，使第3氣體供應源74所供應之載運氣 體附加至由第2載運氣體出口 52b流出之載運氣體，此附加 流量係藉由流量控制器73而變更。 塵力調整部75為了規制在氣體置換裝置5與電漿分析裝 置<5之間之載運氣體之壓力變動，具有第1管75&、第2管 75b、連結第1管75a與第2管75b之連結管75(：、密封氣體供 應源75d、及質量流量控制器（MFC)或流量控制閥等之流量 控制器75e。第1管75a之一端開口 75a，連接於氣體置換裝置 5之第2載運氣體出口 52b，第1管75&之另一端開口連接於 第2導管72之一端72，β第2管7Sb之一端開口 75b•經由流量 控制器75e連接於密封氣體供應源75d，第2管7讣之另一端 開口 75b"連通於大氣中。在本實施型態中，密封氣體供應 源75d係用以供應氬氣作為密封氣體，例如係由儲氣瓶所 構成。第2管75b之内部係經由連結管75c連通於第1管75& 之内部。當第2管75b之内部之壓力因氣體附加裝置7之吸 引載運氣體等而降低時，由密封氣體供應源75d導入第2管 75b之密封氣體之一部分會被引導至第i管75&，以消除其 壓力之降低。 ~ 依據上述分析系統1，在含第1氣體之環境氣體中，藉由 雷射肩熔裝置3使試樣α變成微粒子，以該第1氣趙作為載 氣體將所產生之微粒子由雷射消炼裝置3搬送至氣體 置換裝置5,藉由氣體置換裝置5,將該載運氣體之至少一 部分由第1氣體置換成第2氣體，然後，藉由該載運氣體， 141739.doc 201007165 將微粒子由氣艘置換裝置5搬送至電衆分析裝置6，藉由電 .冑㈣置6，可分析微粒子之構成元素。在本實施型態 中第1氣趙為氦氣，第2氣體為氮氣，故在雷射消溶之際 之環境氣體為比較的熱傳導性高之氦氣，故所產生之微粒 子會變小，可減低微粒子對試樣α之凹痕周邊或載運氣體 流路内面之附著，増多搬送至電漿Ρ之微粒子而提高在電 浆刀析裝置内之原子化、離子化之效率並提高分析感度 及來自電漿Ρ之信號之穩定性。又，因藉由離子化電壓較 _ 低之氬氣’將微粒子導人電漿ρ，故可降低保持電聚ρ所需 之離子化之電力、分析裝置6之負荷，提高電漿Ρ中之離子 密度，使電漿Ρ穩定，並可容易施行分析時之最適測定條 件之選定。 又，在雷射消熔中，即使起因於試樣α之構成成分，而 產生導致電漿分析感度之降低及妨礙測定之氣體成分，也 可藉由氣體置換裝置5之氣鱧置換除去該氣體成分。 [實施例] 作為本發明之實施例，利用上述實施型態之分析系統i 施行微粒子之構成元素之分析，作為比較例，利用由上述 實施型態之分析系統1除去氣體置換裝置5而直接連結雷射 消溶裝置3與電漿分析裝置6之以往之分析系統施行微粒子 之構成元素之分析。 雷射消’溶裝置3使用New Wave Research公司製之UP-213 。 導入 雷射消 熔裝置 3 之 氦氣流 量依序 變化為 6〇〇 ml/min、800 ml/min、1000 ml/min、1200 ml/min、1400 141739.doc -15- 201007165 ml/min、1600 ml/min、1800 ml/min。雷射消炼之重複頻 率為20 Hz，雷射能量係以60%連續振盪，雷射照射圖案為 光柵圖案，雷射束徑為100 μιη，雷射之加熱時間為20秒。 電漿分析裝置6使用GBC公司製之ICP-TOFMS(OPTIMA-9500) ° 導入電漿分析裝置6之氬氣流量呈現一定之800 ml/min。 氣體置換裝置5使用多孔性隔牆52A之材質為矽橡膠多孔 質玻璃，各孔徑為0.1 μιη，氣孔率為70%，壁厚為0.7 mm，外徑為10 mm，長度為420 mm，内管52之兩端附近 部位52B、52C與外管53之材質為石英玻璃，外管53之内 徑為16 mm之氣體置換裝置。 試樣α為30 mm<J)之玻璃標準試樣，使用含銀（Ag)22 ppm、錯（Pb)38.6 ppm、轴（U)37.4 ppm、！它（Tl)15.7 ppm之 試樣。 又，藉由事前之另一試驗，在實施例之系統與比較例之 系統中，比較測定含有微粒子之氣體通過之際之微粒子量 之結果，並未看到有因被吸附於氣體置換裝置5等所帶來 之微粒子之損失。 圖4係表示比較例之測定結果，圖5係表示本發明之實施 例之測定結果。在圖4、圖5中，橫軸表示供應至雷射消熔 裝置3之氦氣之流量，縱軸表示電漿分析裝置6之相對感 度。該相對感度係記載著氦氣之流量為600 ml/min之情形 為1，將依序分別變化為800 ml/min、1000 ml/min、1200 ml/min、1400 ml/min、1600 ml/min、1800 ml/min之情形 141739.doc -16- 201007165 _ 之信號強度除以600 ml/min之情形之信號強度後之值。 由圖4、圖5可確認：相對於在比較例中，試樣a之構成 元素之相對感度因氦氣之流量變動而發生大的變動，在本 發明之實施例中，即使流量發生變動，相對感度之變動也 較少，而可容易施行最適測定條件之選定。 本發明並不限定於上述實施型態或實施例。例如，第i • 氣體可為氦氣以外之氣體，第2氣體也可為氬氣以外之氣 體。 • 又，第1氣體與第2氣體既可如上述實施型態或實施例所 示’為互異之種類，或第1氣體與第2氣體也可均為例如如 氬氣之同一種類。 又，在上述實施例中，雖使藉由氣體附加裝置7導入電 漿分析裝置之第2氣韹之流量呈現一定，但若無必要調節 第2氣體之流量，則無氣體附加裝置7也無妨。 【圖式簡單說明】 圖1係本發明之實施型態之分析系統之構成說明圖； 籲 圖2係本發明之實施型態之氣體置換裝置之構成說明 圃， . 圖3係本發明之實施型態之氣體附加裝置之構成說明 圖； 圖4係表示有關依據比較例之分析系統之微粒子之構成 元素之分析結果之圖；及 圖5係表示有關依據本發明之實施型態之分析系統之微 粒子之構成元素之分析結果之圖。 14I739.doc •17- 201007165 【主要元件符號說明】 1 2 3 3a' 4 5 6 52A 52a 52b 53a 61a' P a 分析系統 第1氣體供應源 雷射消熔裝置 第1載運氣體出口 第2氣體供應源 氣體置換裝置 電漿分析裝置 多孔性隔牆（氣體置換部） 第1載運氣體入口 第2載運氣體出口 第2氣體入口 第2載運氣體入口 電漿 試樣 141739.doc -18·201007165 VI. Description of the Invention: [Technical Field] The present invention relates to, for example, in the semiconductor industry or the electronic parts industry, which is suitable for analysis of metals, semiconductors, ceramics, and glass by using a laser melting device and a plasma analysis device. And methods and systems for adding trace elements or trace impurities to the surface of materials such as plastics. [Prior Art] For example, in Europe, according to the RoHS regulations, materials such as lead, mercury, cadmium, and chromium are prohibited from being contained in materials such as electronic parts. Therefore, for the purpose of confirmation, the laser beam is irradiated to the sample by a laser melting device. One part of the sample becomes a microparticle (aerosol), and the microparticle is introduced into an inductively coupled plasma mass spectrometer (ICP-MS), an inductively coupled plasma luminescence analyzer (ICP-AES), and a microwave inductive plasma mass by a carrier gas. A plasma analysis device such as an analyzer (mip_ms) or a microwave-induced plasma luminescence analyzer (MIP_AES) performs analysis of a trace amount of a trace element or a trace impurity element of the material (see Patent Document 1 and Patent Document 2). Using this type of analysis system, a plurality of trace elements contained in the sample can be analyzed in a single time. Conventionally, in the analysis system as described above, the laser desmelting device and the plasma analyzing device are directly connected, and the ambient gas at the time of laser melting is directly introduced into the plasma analyzing device as the carrier gas of the fine particles. That is, in the system using the conventional laser melting device and the plasma analyzing device, the fine particles are transferred from the laser ablation device to the plasma analyzing device without replacing the carrier gas. Further, it is known that helium or argon is used as a carrier gas used for laser melting, and it is known that argon gas is used as a carrier gas for plasma analysis. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2004-153390. [Patent Document 2] JP-A-2006-153660 SUMMARY OF INVENTION [Problems to be Solved by the Invention] In the case where helium gas is used as the carrier gas, the comparative heat conductivity is higher than that of argon gas, so that the region where the high temperature is exhibited in the laser irradiation is increased. Therefore, the particles generated by laser dissolving will become smaller, so that the adhesion of the particles to the periphery of the dimple formed by the laser de-melting or the inner surface of the carrier gas/body flow path can be reduced, and the transfer to the plasma can be increased. Microparticles improve analytical sensitivity. Further, when the fine particles are increased, it is difficult to perform decomposition and ionization in the plasma, so that the particles become small, and the efficiency of atomization and ionization in the plasma analyzer can be improved, and the analysis sensitivity and the plasma can be improved. Signal stability. However, for the following reasons, it is preferable to use argon as the carrier gas at the time of plasma analysis. That is, the ionization voltage of helium is higher than that of argon, and the power required for ionization to maintain plasma increases, the load of the analyzer increases, and the ion density in the plasma reduce. In addition, when helium gas is used, the plasma becomes unstable compared with argon gas, and the optimum measurement is performed during the analysis. • The selection of conditions is complicated, and it is difficult to measure a plurality of elements with high sensitivity and high precision. Low and damage the speed and simplicity of the analysis. That is, conventionally, the optimization of the analysis using the laser desmelting device and the plasma analyzing device is hindered by the characteristics of the carrier gas. Further, due to the constituent components of the sample, there is a decrease in sensitivity due to laser melting and a change in the gas composition (for example, s 〇 2 et al. 141739.doc 201007165 sulfide) which hinders the measurement. It is an object of the present invention to provide a method and analysis system that solves the above problems. [Technical means for solving the problem] The analysis method of the present invention is characterized in that: in the ambient gas containing the gas, the sample is made into a fine particle by a laser dissolving device; and the aforementioned gas is used as a carrier gas. The fine particles are transported to the gas replacement device by the laser ablation device; and at least a part of the carrier gas is used by the gas replacement device described above! The gas gas is replaced with the second gas; the gas-substituted carrier gas is used to transport the fine particle 2 gas displacement device to the plasma analysis device; and the constituent elements of the fine particles are analyzed by the plasma analyzer. According to the analysis method of the present invention, the first gas is used as the ambient gas of the sample at the time of laser melting, and the fine particles can be transferred to the electricity by the carrier containing the second oxygen replaced by the second gas. Plasma of the slurry analyzer. Further, in the laser ablation, even if the composition of the sample is caused to cause a decrease in the sensitivity of the plasma analysis and the gas component which hinders the measurement, the gas component can be removed by gas replacement by the gas replacement device. The analysis system of the present invention is characterized by comprising: a first gas supply source 'which supplies a first gas; and a laser de-melting device which is provided with a first one supplied by a first gas supply source In the ambient gas of the gas, the sample is made into fine particles by laser ablation, and the first carrier gas outlet that simultaneously flows out of the first gas and the fine particles as the carrier gas is provided, and the second gas is supplied. a second gas supply source; a gas replacement device, 141739.doc -6 - 201007165 having a first carrier gas inlet for introducing the first gas flowing out from the outlet of the first carrier gas Zhao simultaneously with the fine particles, and introducing a second gas inlet for the second gas to which the second gas supply source is supplied, a gas replacement portion for replacing at least a part of the carrier gas with the second gas, and a gas replacement unit for replacing the gas a second carrier gas outlet through which the carrier gas and the fine particles flow simultaneously; and a plasma analysis device having the second carrier gas outlet introduced simultaneously with the fine particles Out of the carrier of the second carrier gas inlet hip luck, generating analysis of the constituent element of the fine particles for analysis with the said carrier gas is simultaneously introduced into the slurry electricity. The method of the invention can be carried out in accordance with the analytical system of the invention. In the present invention, for example, it is preferable to use helium gas for the first gas, and argon gas for the second gas. When the helium gas having a relatively high thermal conductivity is used as the first gas, the fine particles generated in the laser de-melting become small, so that the adhesion of the fine particles to the periphery of the dimple of the sample or the inner surface of the carrier gas flow path can be reduced. The particles are transferred to the plasma, and the efficiency of atomization and ionization in the plasma analyzer is improved, and the analysis sensitivity and the stability of the signal from the plasma are improved. Further, when argon gas is used as the second gas, the fine particles can be introduced into the plasma by the carrier gas containing the argon gas having a low ionization voltage, so that the electric power and the analysis device required for ionization to maintain the plasma can be reduced. The load, the ion density in the plasma of the South, makes the electricity stable, and can be easily selected for the optimum measurement conditions. [Embodiment] [Effects of the Invention] 141739.doc 201007165 According to the present invention, when the plasma analysis of the fine particles by laser melting is performed, the optimization of the analysis conditions can be prevented by the characteristics of the carrier gas of the transported fine particles. It is possible to measure a plurality of elements with high sensitivity and high accuracy and stability without impairing operability, rapidity, and simplicity without impeding the gas component generated by laser melting. The analysis system shown in Fig. 1 includes a second gas supply source 2, a laser ablation device 3, a second gas supply source 4, a gas replacement device 5, a plasma analysis device 6, and a gas addition device 7. In the present embodiment, the first gas supply source 2 is configured to supply helium gas as the first gas, for example, by a gas cylinder. The laser desmelting device 3 can use a known laser ablation device, and has a laser irradiation unit 3a that emits the laser beam L and a sample chamber 3b that houses the sample cassette 1. The first gas system is supplied from the first gas supply source 2 to the sample chamber 3b via the gas outlet 3a. In the sample chamber 3|5, in the ambient gas containing the first gas, the laser beam L is irradiated onto the surface of the sample α, thereby performing laser dissolution of the sample α to make a part of the sample α Become a microparticle. In order to use the second gas as the carrier gas carrier of the microparticles generated by the laser dissolving, the microparticles are simultaneously discharged from the sample chamber 3b with the microparticles. The first carrier gas outlet 3 is formed in the sample chamber 3b. The second gas supply source 4 is for supplying argon gas, for example, by a gas cylinder. As shown in FIG. 2, the gas displacement device 5 can use a known gas displacement device' which is an inner tube 52 including a straight tube having a circular cross section, and a straight tube 53' which covers a circular cross section of the inner tube 52. Both ends of the inner tube 52 are protruded from the outer tube 53. The vicinity of both ends of the outer tube 53 gradually becomes a small diameter and is in close contact with the inner tube 52. 141739.doc -8 - 201007165 - week. The inner tube 52 has a first carrier gas inlet 52a formed at one end, a second carrier gas outlet 52b formed at the other end, and an inner gas flow path between the first carrier gas inlet 52a and the second carrier gas outlet 52b. 52c. The first carrier gas inlet 52a is connected to the first carrier gas outlet 3a'' of the laser desalination apparatus 3 via a pipe (not shown), thereby making the first! The first gas and the fine particles flowing out of the carrier gas outlet 3ai are simultaneously introduced into the gas replacing device 5 from the first carrier gas inlet 52a. The outer tube 53 has a second gas inlet 53a formed on the peripheral wall near one end, an exhaust outlet 53b formed in the peripheral wall near the other end, and an outer side gas flow path 53c between the second gas inlet 53a and the exhaust outlet 53b. . The first carrier gas inlet 52a, the second carrier gas outlet 52b, the second gas inlet 53a, and the exhaust outlet 5 3 b are arranged such that the gas flow direction of the inner gas flow path 5 2 c and the outer gas flow The gas flow directions of the road 53c are opposite to each other. The second gas supply source 4 is connected to the second gas inlet 53a via a pipe (not shown). Thereby, the second gas supplied from the second gas supply source 4 is introduced into the gas replacement device 5 by the second gas inlet 53a'. The portion between the two ends of the peripheral wall of the inner gas passage 52c covering the inner tube 52 is formed so that the porous partition wall 52A' can be diffused by the difference between the first gas and the second gas to make the first gas The inside gas flow path 52c is moved outside, and the second gas is moved into the inner gas flow path 52c. The gas pressure difference between the inner gas flow path 52c and the outer gas flow path 53c, that is, the gas pressure difference between the inner and outer gas flow paths 52c via the porous partition wall 52A can be substantially prevented by the porous partition wall 52A. Therefore, when the first gas and the fine particles are in the same manner as H1739.doc -9- 201007165, the first carrier gas inlet 52a is introduced into the inner tube 52 as the carrier gas 'and flows in the inner gas flow path 52c surrounded by the porous partition wall 52A. The second gas is introduced into the outer tube 53' from the second gas inlet 53a. The outer side gas passage 53c flows in the opposite direction to the flow direction of the first gas around the porous partition wall 52A, and is replaced by gas. In other words, the diffusion due to the partial pressure difference between the first gas and the second gas, in other words, the temperature difference between the first gas and the second gas inside and outside the inner gas channel 52c is a propulsive force, and the first gas is used. Most of the second gas flows outside the inner gas flow path 52c via the porous partition wall 52A, and one of the second gases moves into the inner gas flow path 52c via the porous partition wall 52A. In the inner gas passage 52c, as the first carrier gas inlet 52a flows to the second carrier gas outlet 52b, the concentration of the first gas gradually decreases, and the concentration of the second gas gradually increases. In the outer gas passage 53c, As the second gas inlet 53a flows to the exhaust outlet 53b', the concentration of the second gas gradually decreases, and the concentration of the first gas gradually increases. Therefore, substantially all of the first gas in the carrier gas can be replaced with the second gas. Further, a part of the first gas in the inner tube 52 may not be replaced with the second gas, and a trace amount of the first gas which does not affect the plasma analysis may flow out from the second carrier gas outlet 52b. By appropriately setting the respective pore diameters, porosity, wall thickness, tube diameter, length, shape, inner diameter and shape of the outer tube 53, and the flow rate of the first gas and the second gas, etc., the porous partition wall 52A can be appropriately set. The first gas enthalpy that the carrier gas outlet 52b flows out is controlled to be less than the limit amount which does not adversely affect the analysis of the plasma analyzer 6. In other words, the gas replacement unit composed of the porous barrier 52A may be such that at least a part of the 141739.doc -10 - 201007165 of the microparticle carrier gas can be replaced with the first gas by the first gas. • Therefore, the porous partition wall 52A can constitute a gas displacement portion in which at least a part of the carrier gas of the fine particles is replaced by the first gas into the second gas. Further, the second carrier gas outlet 52b of the inner tube 52 is replaced by the gas, and most of the carrier gas and the fine particles of the second gas are simultaneously discharged from the gas replacement unit. The first gas which is originally the carrier gas and the second gas which is not replaced by the first gas are discharged from the exhaust gas outlet 53b as the exhaust gas "in this case, in the fine particles of the inner gas flow path 52c" The diameter exceeds the outer diameter of the porous partition wall 52A. • It will penetrate the holes or be not captured by the holes, and the diffusion velocity is slower than the gas below the pore diameter, and the inertial force of the gas flow of the diffused gas is very weak. Therefore, most of the fine particles do not move to the outer gas flow path 53c but flow out from the second carrier gas outlet 52b. Therefore, the fine particles introduced simultaneously with the first gas are not reduced or lost. 'The second gas can be supplied to the electric analysing device 6 at the same time.» The respective apertures of the porous partition wall 52A are set to prevent the inner gas flow path from being blocked. The gas passing through the porous partition wall S2A caused by the difference between the pressure of 52c and the pressure of the outer gas flow path 53c is substantially 〇8 μηη to 0.001 μηη. In order to prevent the gas displacement efficiency from decreasing, the size of each device is set to 〇_〇〇1 μιη or more, preferably 〇〇〇2 μηη or more, more preferably 0.02 μηη or more, in order to penetrate the microparticles. Each hole is prevented from being trapped by each hole to reduce the analysis accuracy, or gas movement occurs due to a pressure difference, and δ is less than 〇8 μιη, preferably 〇5 μηη or less, more preferably μιη or less. In the porous partition wall 52, the pore size which does not affect the degree of gas displacement can also be set in the range of 〇8 μπι~〇〇〇1 μηη 141739.doc 201007165 Outside 'substantially only set to 〇_8 Ηη!~〇·〇〇1 pm. The porosity of the porous spacer 52 is not particularly limited, but it is preferably 40% to 80% from the viewpoint of gas displacement efficiency and mechanical strength. The material of the porous partition wall 52 is not particularly limited as long as it satisfies the above conditions. It is preferable to use glass such as quartz or ceramics. For example, porous glass (SPG) can be used. The inner and outer diameters of the portions 52B and 52C near the both ends of the inner tube 52 are equal to the porous partition wall μα and smoothly joined thereto. Further, the entire peripheral wall covering the inner gas passage 52c may be formed as the porous partition wall 5 2 A ' or at least a part of the inner gas passage 5 2 c may be formed as the porous partition wall 52Αβ inner tube 52. The material of the vicinity of the both ends 52Β, 52C and the outer tube 53 is not particularly limited, and may be composed of a plurality of different materials, and the ease of processing and the heating convenience or heat resistance of the first gas introduced into the inner tube 52 are high. In other words, it is preferable to use a metal, a ceramic, or a glass to form a glass such as ceramic or quartz glass. If necessary, a heating mechanism (not shown) may be added to the gas replacing device 5. The heating mechanism is not particularly limited. For example, a band heater heated around the outer tube 53 or an infrared lamp disposed around the outer tube 53 may be provided to control the temperature in the inner and outer tubes 52, 53. The temperature sensor is used and the temperature control device for controlling the heating mechanism according to the detected temperature. The battery analyzer 6 can use a known plasma analyzer, and in the present embodiment, the plasma torch 61 and the analyzer 62 are provided as ICP-MS. The type of the plasma analyzer 6 is not particularly limited, and for example, lcp_AES, MIP-MS, or MIP-AES can also be used. The plasma torch 61 has a center tube 61a, 141739.doc 201007165 One end of the center tube 61a is formed as a second carrier gas inlet 61a. The carrier gas system flowing out of the second carrier gas outlet 52b of the gas replacing device 5 and the fine particles are simultaneously introduced into the plasma analyzing device 6 by the second carrier gas inlet 61a. The gas system containing the fine particles introduced by the center tube 61a is converted into the analysis plasma P of the constituent elements of the fine particles by the high-frequency coils and the like, and the mass analysis of the constituent elements is performed in the analysis unit 62. Further, the plasma gas for generating the plasma p may be introduced into the plasma torch 61 from the gas inlet port 6, and the plasma gas is preferably the same gas as the second gas boat. The gas adding device 7 is provided with a carrier gas between the gas replacing device 5 and the plasma analyzing device 6. In other words, the gas adding device 7 includes a first duct 71, a second duct 72 connected to the first duct 71, a flow rate controller 73 such as a mass flow controller (MFC) or a flow rate control valve, and a third gas supply source 74. And the pressure adjusting portion 75 » The one end opening 71' of the first duct 71 is connected to the second carrier gas inlet 61a' of the plasma analyzer 6. A throttle portion 71a and a diffusion portion 71b connected to the outlet of the throttle portion 71a are formed in the first duct 71. The other end opening 71 of the first duct 71 is connected to the third gas supply source 74 via the flow rate controller 73. The one end 72 of the second duct 72 passes through the first tube 75a of the pressure adjusting unit 75 to the gas replacing device 5 2, the carrier gas outlet 52b, the other end 72" of the second conduit 72 leads to a discharge region of the carrier gas near the outlet of the throttle portion 71a. In the present embodiment, the third gas supply source 74 is used for supply The argon gas pressurized as the carrier gas is, for example, composed of a gas cylinder, and the pressure head caused by the discharge of the argon gas supplied from the third gas supply source 74 by the throttle portion 71 a is reduced by the gas replacement device 5 The second carrier gas outlet 52b flows 141739.doc 13 201007165 The carrier gas is sucked into the first conduit 71. That is, the gas adding device 7 constitutes an aspirator. Thereby, the third gas supply source 74 is supplied. The carrier gas is added to the carrier gas flowing out from the second carrier gas outlet 52b, and the additional flow rate is changed by the flow rate controller 73. The dust force adjusting unit 75 is regulated in the gas replacing device 5 and the plasma analyzing device < Pressure of the carrier gas The force varies, and includes a first pipe 75 & a second pipe 75 b, and a connecting pipe 75 (:, a sealed gas supply source 75 d, a mass flow controller (MFC), or a flow rate control valve that connects the first pipe 75 a and the second pipe 75 b The flow controller 75e of the first tube 75a is connected to the second carrier gas outlet 52b of the gas replacement device 5, and the other end of the first tube 75& is open to the end 72 of the second conduit 72, β The one end opening 75b of the second tube 7Sb is connected to the sealed gas supply source 75d via the flow rate controller 75e, and the other end opening 75b" of the second tube 7 is connected to the atmosphere. In the present embodiment, the sealed gas supply source 75d The argon gas is supplied as a sealing gas, for example, by a gas cylinder. The inside of the second pipe 75b communicates with the inside of the first pipe 75& via the connecting pipe 75c. The pressure inside the second pipe 75b is caused by When the gas supply device 7 is lowered by the suction of the carrier gas or the like, a part of the sealing gas introduced into the second pipe 75b by the sealing gas supply source 75d is guided to the i-th tube 75& to eliminate the pressure drop. System 1, in the presence of the first gas In the gas, the sample α is made into fine particles by the laser shoulder melting device 3, and the generated fine particles are transferred from the laser refining device 3 to the gas replacing device 5 by the first gas Zhao as a carrier gas, by the gas The replacement device 5 replaces at least a part of the carrier gas with the first gas, and then transports the fine particles from the gas displacement device 5 to the battery analysis device 6 by the carrier gas 141739.doc 201007165. By means of electricity (胄) (6), the constituent elements of the microparticles can be analyzed. In the present embodiment, the first gas is a helium gas, and the second gas is nitrogen gas. Therefore, since the ambient gas at the time of laser dissolution is a comparatively high heat conductivity, the generated fine particles are small. Decreasing the adhesion of the fine particles to the periphery of the dent of the sample α or the inner surface of the carrier gas flow path, and transferring the fine particles to the plasma 而 to improve the efficiency of atomization and ionization in the plasma knife-carrying device and improve the analysis sensitivity and The stability of the signal from the plasma. Further, since the fine particles are guided to the plasma ρ by the argon gas having a lower ionization voltage, the ionization power required to maintain the electropolymerization ρ and the load of the analyzer 6 can be reduced, and the plasma is increased. The ion density makes the plasma enthalpy stable, and the optimum measurement conditions for the analysis can be easily performed. Further, in the laser ablation, even if the component of the sample α is caused to cause a decrease in the sensitivity of the plasma analysis and a gas component which hinders the measurement, the gas can be replaced by the gas replacement device 5 to remove the gas. ingredient. [Embodiment] As an embodiment of the present invention, analysis of constituent elements of fine particles is performed by the analysis system i of the above-described embodiment, and as a comparative example, the gas replacement device 5 is directly connected by the analysis system 1 of the above-described embodiment. The analysis system of the laser dissolving device 3 and the plasma analyzing device 6 performs analysis of constituent elements of the fine particles. The laser eliminator 3 uses UP-213 manufactured by New Wave Research. The helium flow rate introduced into the laser melting device 3 is sequentially changed to 6〇〇ml/min, 800 ml/min, 1000 ml/min, 1200 ml/min, 1400 141739.doc -15- 201007165 ml/min, 1600 Ml/min, 1800 ml/min. The repetition rate of laser refinement is 20 Hz, the laser energy is continuously oscillated at 60%, the laser illumination pattern is a grating pattern, the laser beam diameter is 100 μηη, and the laser heating time is 20 seconds. The plasma analyzer 6 was introduced into the plasma analyzer 6 using an ICP-TOFMS (OPTIMA-9500) manufactured by GBC Co., Ltd., and the argon gas flow rate was set to 800 ml/min. The gas replacement device 5 uses a porous partition wall 52A made of ruthenium rubber porous glass, each having a pore diameter of 0.1 μm, a porosity of 70%, a wall thickness of 0.7 mm, an outer diameter of 10 mm, and a length of 420 mm, and an inner tube. The material 52B, 52C and the outer tube 53 near the two ends of the 52 are made of quartz glass, and the inner tube 53 has a gas displacement device of 16 mm. Sample α is a glass standard sample of 30 mm < J), using silver (Ag) 22 ppm, wrong (Pb) 38.6 ppm, and shaft (U) 37.4 ppm, ! It (Tl) is a sample of 15.7 ppm. Further, by the other test beforehand, in the system of the embodiment and the system of the comparative example, the result of measuring the amount of the fine particles passing through the gas containing the fine particles was not observed, and the cause was not adsorbed to the gas replacing device 5. The loss of the particles caused by the etc. Fig. 4 shows the measurement results of the comparative examples, and Fig. 5 shows the measurement results of the examples of the present invention. In Figs. 4 and 5, the horizontal axis represents the flow rate of helium gas supplied to the laser ablation device 3, and the vertical axis represents the relative sensitivity of the plasma analyzer 6. The relative sensitivity system records that the flow rate of helium gas is 600 ml/min, and will be changed to 800 ml/min, 1000 ml/min, 1200 ml/min, 1400 ml/min, and 1600 ml/min, respectively. 1800 ml/min 141739.doc -16- 201007165 _ The signal strength is divided by the signal strength after 600 ml/min. 4 and 5, it can be confirmed that, in the comparative example, the relative sensitivity of the constituent elements of the sample a largely fluctuates due to the flow rate fluctuation of the helium gas, and in the embodiment of the present invention, even if the flow rate fluctuates, The relative sensitivity is also less varied, and the selection of the optimum measurement conditions can be easily performed. The present invention is not limited to the above embodiment or embodiment. For example, the i-th gas may be a gas other than helium, and the second gas may be a gas other than argon. Further, the first gas and the second gas may be different from each other as described in the above embodiment or the embodiment, or the first gas and the second gas may be of the same type as, for example, argon gas. Further, in the above embodiment, the flow rate of the second gas introduced into the plasma analyzer by the gas adding device 7 is constant, but if it is not necessary to adjust the flow rate of the second gas, the gasless device 7 may be used. . BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a configuration diagram of an analysis system according to an embodiment of the present invention; FIG. 2 is a configuration diagram of a gas displacement device according to an embodiment of the present invention, and FIG. 3 is an embodiment of the present invention. FIG. 4 is a view showing an analysis result of constituent elements of fine particles according to an analysis system of a comparative example; and FIG. 5 is a view showing an analysis system according to an embodiment of the present invention. A graph of the analysis results of the constituent elements of the microparticles. 14I739.doc •17- 201007165 [Description of main component symbols] 1 2 3 3a' 4 5 6 52A 52a 52b 53a 61a' P a Analysis system 1st gas supply source Laser melting device 1st carrier gas outlet 2nd gas supply Source gas replacement device Plasma analysis device Porous partition wall (gas replacement unit) First carrier gas inlet Second carrier gas outlet Second gas inlet Second carrier gas inlet plasma sample 141739.doc -18·